CN108864472B - Ultrathin microporous silk fibroin film, preparation method and application - Google Patents
Ultrathin microporous silk fibroin film, preparation method and application Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/22—Polypeptides or derivatives thereof, e.g. degradation products
- A61L27/227—Other specific proteins or polypeptides not covered by A61L27/222, A61L27/225 or A61L27/24
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/56—Porous materials, e.g. foams or sponges
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
- C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
- C08J2201/0504—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being aqueous
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2389/00—Characterised by the use of proteins; Derivatives thereof
Abstract
The invention discloses an ultrathin microporous silk fibroin membrane, a preparation method and application. The method comprises the following steps: dissolving silk fibroin fiber or powder in a solvent, and filtering to obtain a high-concentration silk fibroin solution; directly or after diluting the silk fibroin liquid into different concentrations, slowly injecting the silk fibroin liquid into the high-concentration mixed salt solution by adopting an injection device, and quickly diffusing the silk fibroin liquid on the liquid surface to form a film. The thickness of the single-layer film is only 0.4 mu m, the thickness of the film is regulated and controlled by the number of winding layers, the porosity of the film is high, and micropores with the pore diameter of 0.5-1.5 mu m are fully distributed. The invention prepares the ultrathin micropore silk fibroin film by the interface diffusion principle, and has simple and efficient process, high film forming quality and good performance. The membrane has wide application prospect in the fields of biomedical materials and filtering materials.
Description
Technical Field
The invention relates to a natural polymer membrane material, in particular to an ultrathin microporous silk fibroin membrane, a preparation method and application, and belongs to the field of natural polymer materials.
Background
The silk fibroin is a natural polymer with wide sources, has excellent biocompatibility and biodegradability, and can be regenerated to be made into various forms such as fibers, films, gels, sponges and the like so as to meet the requirements of various applications. Wherein, the silk fibroin film has great application value in the aspects of biomedical materials and filtering materials. For example, 2009 (CN 101879098A) discloses an artificial eardrum using silk protein and a method for manufacturing the same, wherein a silk protein solution is dried to form a silk membrane, which is used as an artificial eardrum and a patch. For example, 2016 (CN 106283399a) discloses a modified nanofiber membrane with ordered arrangement, and its preparation and application, wherein silk fibroin, collagen and polycaprolactone are mixed and dissolved, and then the nanofiber membrane is prepared by electrostatic spinning, and used as a cell culture scaffold. For example, patent 2014 (CN 103611192a) discloses a partially reduced graphene oxide and silk fibroin composite membrane, and a preparation method and application thereof, wherein the partially reduced graphene and silk fibroin liquid are mixed and then cast on a polytetrafluoroethylene flat plate to prepare the composite membrane, so that the tensile property and the toughness of the silk fibroin membrane are improved. For example, a 2017 patent (CN 106668940A) discloses a silk fibroin bilayer membrane, a preparation method and an application thereof, wherein a silk fibroin evaporation membrane is prepared firstly, then an electrostatic spinning membrane is prepared on the surface of the evaporation membrane, and the finally prepared bilayer membrane is used as an artificial periosteum imitation. For example, patent (CN 104474914a) in 2015 discloses a nanofiber membrane containing silk fibroin and a preparation method thereof, wherein a fibroin solution containing carbon nanotubes is prepared into the nanofiber membrane by an electrostatic spinning method for microfiltration and nanofiltration of water. Therefore, the current methods for preparing the silk fibroin membrane mainly comprise a solution drying method and an electrostatic spinning method, and the problems of low efficiency, poor membrane performance and the like generally exist. In 5 months 2018, Zhang Lin research team at university of Zhejiang at Science 360 th stage 518-521 reported that "polyamine membranes with nanoscale membrane structures for water purification" revealed the "reaction-diffusion" process mechanism of interfacial polymerization "Tuoling structure" membrane. The invention prepares the ultrathin microporous silk fibroin film by the rapid diffusion of the silk fibroin liquid at the interface of the salt solution.
Disclosure of Invention
The invention aims to provide an ultrathin microporous silk fibroin film, which is ultrathin and soft, and the thickness of a single layer is only 0.4 mu m; the membrane has high porosity, is fully distributed with micropores with the pore diameter of 0.5-1.5 mu m, has good mechanical property, filtering property and biocompatibility, and has good application prospect in the aspects of biomedical bracket materials and micro-nano filtering materials.
The invention also aims to provide a preparation method of the ultrathin microporous silk fibroin membrane, which is mainly characterized in that the membrane is formed by fast diffusion of the silk fibroin liquid on the liquid-gas interface of a salt solution, the thickness, the pore and the like of the membrane can be conveniently regulated, and the method is simple, convenient and efficient and comprises the following steps:
s1, dissolving silk fibroin fibers or powder in a solvent, and filtering to obtain a high-concentration silk fibroin solution;
s2, directly or after diluting the silk fibroin solution obtained in the step S1 into different concentrations, slowly injecting the silk fibroin solution into a high-concentration mixed salt solution by using an injection device, and quickly diffusing the silk fibroin solution to form a film;
and S3, removing the silk fibroin membrane obtained in the step S2, washing with pure water, reeling, collecting and drying to obtain the ultrathin microporous silk fibroin membrane.
Further, the preparation method of the ultrathin microporous silk fibroin membrane comprises the following specific steps:
a. dissolving silk fibroin fibers or powder in 5-7 wt% of LiBr/acetone solvent, and then filtering to obtain a high-concentration silk fibroin solution;
b. b, directly or after diluting the silk fibroin solution obtained in the step a into different concentrations, slowly injecting the solution into a salt solution with the concentration of 30-40 wt% by using an injection device, wherein the injection height is 1-20 mm higher than the liquid level of the salt solution, and quickly diffusing the silk fibroin solution on the liquid-gas interface of the salt solution to form a film;
c. and (c) removing the silk fibroin membrane obtained in the step (b), washing with pure water, reeling, collecting and drying to obtain the ultrathin microporous silk fibroin membrane.
Further, the salt is one or more of sodium sulfate, sodium chloride, ammonium sulfate and ammonium dihydrogen phosphate.
Further, the ultrathin microporous silk fibroin film with a single-layer structure, a double-layer structure and a multi-layer structure is obtained through coiling control.
Further, the ultrathin microporous silk fibroin film is dried at 25-80 ℃.
The ultrathin microporous silk fibroin membrane can be applied to cell culture scaffolds and blood, water and air filtration.
The invention has the beneficial effects that: the silk fibroin membrane structure of the invention is different from electrostatic spinning fiber membranes and solution drying membranes, and the membrane has the advantages of ultra-thin, softness, high microporosity and the like, and has good mechanical property, filtering property and biocompatibility. The preparation method of the invention utilizes the principle of interfacial diffusion to enable the silk fibroin liquid to be rapidly diffused and formed into a film on the liquid-gas interface of the salt solution, and compared with an electrostatic spinning method and a solution drying method, the preparation method has the advantages of simple and efficient process, high film forming quality and easy regulation and control of the structure of the film.
Drawings
The invention will be further described with reference to the accompanying drawings and examples, in which:
fig. 1 is a surface SEM image of the silk fibroin membrane of example 2;
fig. 2 is a stress-strain plot of the silk fibroin membrane of example 1.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and examples, but the present invention is not limited thereto.
Example 1
(1) Putting 5g of silk fibroin fibers into 100ml of 5 wt% LiBr/acetone solvent, oscillating at constant temperature of 37 ℃ for 48h, and filtering the dissolved product to obtain about 25 wt% of silk fibroin liquid;
(2) slowly injecting the silk fibroin solution into 30 wt% sodium sulfate solution by a micro-injection pump, wherein an injection nozzle is 1mm higher than the liquid level of the sodium sulfate solution, and the silk fibroin solution is rapidly diffused at a liquid-gas interface to form a film;
(3) and removing the silk fibroin film, washing with pure water, rolling the double-layer film by using a roller, and drying at 25 ℃ to obtain the double-layer ultrathin microporous silk fibroin film with the thickness of about 1 mu m. Referring to attached figure 1, which is a surface SEM image of the double-layer silk fibroin film prepared in this example, it can be seen that countless micropores are uniformly distributed on the film, and the pore diameter is 0.5-1.5 μm.
Example 2
(1) Putting 5g of silk fibroin fibers into 100ml of 7 wt% LiBr/acetone solvent, oscillating at constant temperature of 37 ℃ for 24h, and filtering the dissolved product to obtain about 20 wt% of silk fibroin liquid;
(2) diluting the silk fibroin liquid to 10 wt% with water, slowly injecting the diluted silk fibroin liquid into a mixed solution of 40 wt% of sodium sulfate/ammonium dihydrogen phosphate through a micro injection pump, wherein an injection nozzle is 20mm higher than the liquid level of the sodium sulfate/ammonium dihydrogen phosphate solution, and the silk fibroin liquid is rapidly diffused at a liquid-gas interface to form a film;
(3) and (3) removing the silk fibroin film, washing with pure water, rolling the single-layer film by using a roller, and drying at 80 ℃ to obtain the single-layer ultrathin microporous silk fibroin film with the thickness of about 0.4 mu m. Countless micropores are uniformly distributed on the membrane, and the aperture is 0.5-1.5 μm.
Example 3
(1) Putting 5g of silk fibroin fibers into 100ml of 6 wt% LiBr/acetone solvent, oscillating at constant temperature of 37 ℃ for 24h, and filtering the dissolved product to obtain about 22 wt% of silk fibroin liquid;
(2) slowly injecting the silk fibroin solution into 30 wt% sodium chloride solution through a micro injection pump, wherein an injection nozzle is 10mm higher than the liquid level of the sodium chloride solution, and the silk fibroin solution is rapidly diffused at a liquid-gas interface to form a film;
(3) and removing the silk fibroin film, washing with pure water, rolling the three-layer film by using a roller, and drying at 50 ℃ to obtain the three-layer ultrathin microporous silk fibroin film with the thickness of about 1.4 mu m. Countless micropores are uniformly distributed on the membrane, and the aperture is 0.5-1.5 μm.
Example 4
(1) Putting 5g of silk fibroin fibers into 100ml of 7 wt% LiBr/acetone solvent, oscillating at constant temperature of 37 ℃ for 24h, and filtering the dissolved product to obtain about 20 wt% of silk fibroin liquid;
(2) slowly injecting the silk fibroin solution into 35 wt% of sodium sulfate/ammonium sulfate mixed solution through a micro-injection pump, wherein an injection nozzle is 15mm higher than the liquid level of the sodium sulfate/ammonium sulfate solution, and the silk fibroin solution is rapidly diffused at a liquid-gas interface to form a film;
(3) and (3) removing the silk fibroin film, washing with pure water, rolling the single-layer film by using a roller, and drying at 37 ℃ to obtain the single-layer ultrathin microporous silk fibroin film with the thickness of about 0.7 mu m. Countless micropores are uniformly distributed on the membrane, and the aperture is 0.5-1.5 μm.
Example 5
(1) Putting 5g of silk fibroin fibers into 100ml of 7 wt% LiBr/acetone solvent, oscillating at constant temperature of 37 ℃ for 24h, and filtering the dissolved product to obtain about 20 wt% of silk fibroin liquid;
(2) diluting the silk fibroin liquid to 15 wt% with water, slowly injecting the diluted silk fibroin liquid into 30 wt% sodium sulfate/sodium chloride solution through a micro injection pump, wherein an injection nozzle is 5mm higher than the liquid level of the sodium sulfate/sodium chloride solution, and the silk fibroin liquid is rapidly diffused at a liquid-gas interface to form a film;
(3) and removing the silk fibroin film, washing with pure water, rolling the double-layer film by using a roller, and drying at 25 ℃ to obtain the double-layer ultrathin microporous silk fibroin film with the thickness of about 1.2 mu m. Countless micropores are uniformly distributed on the membrane, and the aperture is 0.5-1.5 μm. Referring to fig. 2, which is a tensile stress-strain curve diagram of the silk fibroin film of the present example, it can be seen that the flexibility and toughness of the film are good.
Claims (10)
1. An ultrathin microporous silk fibroin membrane is characterized in that: the silk fibroin film is of a single-layer or multi-layer structure, the thickness of the single-layer film is 0.4-0.7 mu m, and the aperture of the film is 0.5-1.5 mu m; the preparation method of the ultrathin microporous silk fibroin membrane comprises the following steps:
s1, dissolving silk fibroin fibers or powder in a solvent, and filtering to obtain a high-concentration silk fibroin solution;
s2, directly or diluting the silk fibroin solution obtained in the step S1 into different concentrations, and then slowly injecting the silk fibroin solution into the surface of a high-concentration salt solution by using an injection device, wherein the silk fibroin solution is rapidly diffused into a film, and the salt is one or more of sodium sulfate, sodium chloride, ammonium sulfate and ammonium dihydrogen phosphate;
and S3, removing the silk fibroin membrane obtained in the step S2, washing with pure water, reeling, collecting and drying to obtain the single-layer or multi-layer ultrathin micropore silk fibroin membrane.
2. A method for preparing the ultra-thin microporous silk fibroin membrane of claim 1, comprising the steps of:
s1, dissolving silk fibroin fibers or powder in a solvent, and filtering to obtain a high-concentration silk fibroin solution;
s2, directly or diluting the silk fibroin solution obtained in the step S1 into different concentrations, and then slowly injecting the silk fibroin solution into the surface of a high-concentration salt solution by using an injection device, wherein the silk fibroin solution is rapidly diffused into a film, and the salt is one or more of sodium sulfate, sodium chloride, ammonium sulfate and ammonium dihydrogen phosphate;
and S3, removing the silk fibroin membrane obtained in the step S2, washing with pure water, reeling, collecting and drying to obtain the ultrathin microporous silk fibroin membrane.
3. The method for preparing the ultrathin microporous silk fibroin membrane as claimed in claim 2, is characterized in that: in the step S1, the solvent is a LiBr/acetone binary solvent system, and the concentration of LiBr is 5-7 wt%.
4. The method for preparing the ultrathin microporous silk fibroin membrane as claimed in claim 2, is characterized in that: and in the step S2, the fibroin solution is diluted or not diluted by pure water, and the concentration is 10-25 wt%.
5. The method for preparing the ultrathin microporous silk fibroin membrane as claimed in claim 2, is characterized in that: the concentration of the salt solution in the step S2 is 30-40 wt%.
6. The method for preparing the ultrathin microporous silk fibroin membrane as claimed in claim 2, is characterized in that: and in the step S2, the nozzle of the injection device is not immersed in the saline solution, and the injection height is 1-20 mm higher than the liquid level of the saline solution.
7. The method for preparing the ultrathin microporous silk fibroin membrane as claimed in claim 2, is characterized in that: and the silk fibroin solution injected in the step S2 is diffused on the liquid-gas interface of the salt solution to form a film.
8. The method for preparing the ultrathin microporous silk fibroin membrane as claimed in claim 2, is characterized in that: and S3, controlling the coiling layer number of the silk fibroin film to obtain the ultrathin microporous silk fibroin film with a single-layer or multi-layer structure.
9. The method for preparing the ultrathin microporous silk fibroin membrane as claimed in claim 2, is characterized in that: in the step S3, the drying temperature is 25-80 ℃.
10. The use of an ultra-thin microporous silk fibroin membrane as claimed in claim 1 or obtained by the method of claim 2, characterized by being applied to water and air filtration.
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| CN110010370B (en) * | 2019-04-29 | 2020-11-10 | 西南大学 | Flexible all-solid-state electrode or super capacitor and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2012082246A (en) * | 2010-10-06 | 2012-04-26 | Hitachi Chemical Co Ltd | Silk fibroin porous body, and method for manufacturing the same |
| CN103536962A (en) * | 2012-09-17 | 2014-01-29 | 浙江星月生物科技股份有限公司 | Silk fibroin film insoluble in water as well as preparation and application of silk fibroin film |
| CN106000134A (en) * | 2016-07-08 | 2016-10-12 | 天津工业大学 | Temperature-sensitive filtering membrane with small pore size distribution and preparation method thereof |
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| EP3231846A1 (en) * | 2003-04-10 | 2017-10-18 | Tufts University | Concentrated aqueous silk fibroin solution and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012082246A (en) * | 2010-10-06 | 2012-04-26 | Hitachi Chemical Co Ltd | Silk fibroin porous body, and method for manufacturing the same |
| CN103536962A (en) * | 2012-09-17 | 2014-01-29 | 浙江星月生物科技股份有限公司 | Silk fibroin film insoluble in water as well as preparation and application of silk fibroin film |
| CN106000134A (en) * | 2016-07-08 | 2016-10-12 | 天津工业大学 | Temperature-sensitive filtering membrane with small pore size distribution and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| Polyamide membranes with nanoscale Turing structures for water purification;Tan et al.;《SCIENCE》;20180504;第360卷;第518-521页 * |
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